The first comprehensive structural study of the Ni–U–O system is reported. Single crystals of α-NiUO4, β-NiUO4, and NiU3O10 were synthesized, and their structures were refined—using synchrotron single-crystal X-ray diffraction data supported by X-ray absorption spectroscopic measurements. α-NiUO4 adopts an orthorhombic structure in space group Pbcn and is isostructural to CrUO4 containing corrugated two-dimensional (2D) layers of corner-sharing UO6 polyhedra and edge-sharing one-dimensional (1D) zigzag α-PbO2 rutile-like chains of NiO6 polyhedra in the [001] direction. β-NiUO4 is isostructural to MgUO4 and has an orthorhombic structure in space group Ibmm, which contains alternating 1D chains of edge-sharing UO6 and NiO6 polyhedra in the [001] direction as in regular TiO2 rutile. NiU3O10 forms a triclinic structure in space group P1 and is isostructural with CuU3O10, where it forms a three-dimensional (3D) framework structure built through a mixture of UO6 and UO7 polyhedra in which the NiO6 polyhedra si...